Method of applying a coating



,molecular weight to protect and/or decorate 2,978,354 METHOD OF APPLYING A COATING David K. Lesser, P.O. Box 1642, Wilmington, Del. No Drawing. Filed Mar. 18, 1958, Ser. No. 722,140 7 Claims. (Cl. 117-47) This invention relates to a method of applying aprotective and decorative coating, and, more particularly,

relates to a method of applying a low-molecular weight resin as a coating.

It has been found advantageous to apply coatings or films of various low-molecular weight resins to a wide variety of materials and then polymerize them to a high the materials. Examples of resins commercially used in such coatings or films are epoxy resins, acrylics, phenolformaldehydes, and unsaturated polyesters. These resins are cured or polymerized, for example, by the application resin and a strong catalyst has an extremely short pot life, it gels soon after the catalyst is added to the resin. These mixtures must, therefore, be applied very soon after they are mixed to prevent them from gelling in the apparatus used for applying them to the base material. Batches of resin and catalyst can, therefore, be premixed only in the quantities which are small enough to be almost immediately applied to the substrate.

period or requires,

' catalyst spray gun which simultaneously sprays the uricatalyzed polyester is applied.

resin and the catalyst on the substrate thereby mixing them in the air on their way to the substrate. However, it is difiicult to control the ratio of resin to catalyst, and the spraying equipment is complicated and expensive.

A recently developed technique for applying polyester coatings involves depositing an organic-soluble catalyst 1n a ground coat upon the substrate before the The organic-soluble catalyst is either dissolved alone prior to application in -an organic solvent or organic plasticizer, or it is dissolved the substrate when the solvent along with some other material that can form afilm upon evaporates. After the catalyst mixture dries, a substantial amount remains upon the surface evaporated,

of the substrate either alone or in a mixture with modifying agents. Even though the solvent has a ground coat that can be seen and felt remains upon the surface of the substrate. When a nonairinhibited polyester is applied over this substantial ground "coat, it, therefore, combines with -ing almost immediately which avoids most of the problems resulting from the short pot life of the resin and catalyst mixtures.

this type have been it and starts polymeriz- However, substantial ground coats of successfully applied only with organicsoluble catalystswhich are usuallyrather weak and re- 'quire prolonged curing periods or exposure to elevated temperatures during curing. Furthermore, these organicas a coating, which able catalysts and 2,978,354 Patented Apr. 4, 1961 2 soluble catalysts are unstable particularly when these storing temperatures cannot be maintained sutficiently depressed. Moreover, these organic-soluble catalysts are sults achieved tend to be unpredictable.

An object of this invention is to provide a simple and reliable method of applying a low-molecular weight resin utilizes inexpensive and readily availprovides rapid curing at normal room temperatures to produce coatings of good physical properties.

the catalyst present to be seen or felt. Suitable wetting agents are mixed into the aqueous soluby applying a coating of uncatalyzed resin over the apparently consumed and vanished layer of water-soluble .catalyst. However, in some unexplainable manner,

enough of the effect of the catalyst remains to polymerize securely anchored to and substrate.

The following is a flow diagram describing the steps of the aforementioned method:

I Substrate I Aqueous Solution of water soluble catalyst Ground coat of water soluble catalyst Ground coat dried and apparently vanished Unsaturated polyester saturated polyester upon dried ground coat I Polymerlzlng I Polymer-lied coating of polyester Water soluble catalysts have many desirable proper ties including stability in storage, relative cheapness and ready availability. the water-soluble catalysts are only about to as expensive as corresponding organic-soluble catalysts. For example, the cost of some representative water-soluble catalysts is approximately 15 cents per pound in comparison to the three dollars per pound approximate cost of corresponding organic-soluble catalysts. Moreover, these water-soluble catalysts cure or polymerize at rates which are approximately 3 times as fast at normal room temperatures as the curing rates of organic-soluble catalysts.

The following is a table showing examples of several catalysts that can be used for curing coating resins.

TABLE A Type Resin Catalyst Unsaturated polyester Hydrogen peroxide.

Sodium hypochlorite. Boron fluoride.

Boron chloride. Aluminum chloride. Sodium persuliate.

The following general techniques have been successfully practiced in utilizing water-soluble catalysts for polymerizing unsaturated polyesters.

General Example 1 Thirty percent hydrogen peroxide is applied as a thin film on a nonabsorbent substrate, for example, linoleum, and allowed to dry until it disappears completely and leaves the linoleum dry and uncoated as far as sight and touch can detect. An uncatalyzed polyester which is not air inhibited is then applied to the substrate. Surprisingly enough, the resin begins to immediately polymerize on contact with the substrate to form a hard, tough coating even though there was no apparent trace of the catalyst present upon the linoleum.

General Example II If the water solution of the catalyst is too strong, or if it does not evaporate rapidly enough, it can be thinned with a waterarniscible organic solvent. This mixture may range widely from approximately 2 parts by weight of catalyst to 98 parts by weight of solvent to approximately 2 parts by weight of solvent to 98 parts by weight of catalyst. Furthermore, the addition of certain organic solvents may further increase the handling safety of the catalyst as well as improving its wetting ability.

General Example Ill General Example IV The water solution including the catalyst can be mixed with a water-thinnable latex to retard the penetration of the catalyst into a porous substrate, such as wood. The dry latex film also retards the penetration of the polyester into the substrate. Examples of such water-thinna- In spite of these advantages, most of ble latexes are polyvinyl acetate, acrylic, isobutylenestyrene, etc. From about 1 part by weight of catalyst with 99 parts by weight of latex to about 1 part by weight of latex with 99 parts by weight of catalyst may be used. Organic plasticizers and solvents may also be added to the catalyst-latex mixture.

General Example V The catalyst may be mixed with water-soluble film formers such as water glass, animal glue, polyvinyl alcohol, casein, etc., to provide films which retard the penetration of catalyst and resin into porous substrates.

General Example V1 The aqueous phase of an emulsion whether it is continuous or discontinuous may be intermixed with the catalyst to provide films which retard penetration into the substrate. Such emulsions are, for example, nitrocellulose, shellac, resin, etc.

General Example VII Organic solvent solutions of film formers which tolerate a substantial percentage of water even though they are not completely water-soluble can also be mixed into the catalyst to retard penetration into the substrate. Some of these materials are, for example, ethylcellulose, polyvinyl butyral, soluble nylon, etc. Approximately from 1 part of catalyst by weight with 99 parts of film former solution to 75 parts by weight of catalyst with 20 parts by weight of the film former solution may be utilized.

Somewhat similar methods of application may be utilized to induce polymerization when the aqueous catalyst is applied over an uncatalyzed film of resin, for example, polyester, instead of under the uncatalyzed resin film. Three-coat systems, including a first coat of uncatalyzed polyester, a second coat of water-soluble catalyst and a third coat of uncatalyzed polyester have been also found to rapidly polymerize into an extremely hard and durable coating.

Specific coating thicknesses and drying times of the water-soluble reactive ground coats are difiicult to specify because these factors are influenced by the type of catalyst, its concentration, reactivity of the corresponding resin, and the curing temperature. However, with a water-soluble catalyst consisting of 5 parts by weight of 30% hydrogen peroxide and 10 parts by weight of polyvinyl acetate, for example, Polyco 117-SS made by the Borden Company, the wet film thickness of the reactive ground coat should be approximately one-half to two-thirds of the total thickness of a polyester top coat. When this type of ground coat is applied to fir plywood, it dries and is in condition ready to initiate polymerization of a polyester top coat in as little as 15 minutes at room temperature. In spite of the fact that the hydrogen peroxide apparently vanishes after drying, the ground coat remains in condition for reaction with a resin top coat for as long as approximately 3 days if maintained somewhere near normal room temperatures.

Although all of the reasons for the potency of these invisible and apparently non-existent catalysts are not completely understood, it is believed that there are enough of the polymerizing free radicals remaining upon the substrate to initiate polymerization of the later deposited resin coating, even though they cannot be seen or felt.

Various examples of coatings formed by specific water-soluble catalyst ground coats and resins as applied to specific substrates are given in the following to demonstrate how this technique is carried out for coating many diiferent kinds of materials.

Specific Example] s Specific Example 4 Bubstratelinoleum i i D Substrate-cork floor tile 1 Groundcoat30% hydrogen peroxide (acid stabilized) r r i Brush mil wet iilm, air dry 55 hour. GROUNDCOAT TOP COAT Parts Manufacturer Designation Constituents Weightor Parts by Volume Manufacturer Designation Constituents Weight or Volume sodium hlypochlorlte" 5 Dow Methylcel,400cpmethylce ulose 34 Amer. Cyanarnid. Laminac 4110-4-6. Urlrsaiturlzted 7.6 water 95 0 YES 01'. D c gi' i f i fi?f: gtf ggigffiifgi? Application Procedure-Kniiecoat one mil .wet film, dry two hours at thanate room temperature.

A s t TOP ooA'r Application Procedure-Brush one mil wet film, air dry overnight at roomtemperature. y 7. .7 a1 8 S ifi E l 2 Manufacturer Designation Constituents Vlliy v v g 0 me Substrate-sanded Fir plywood FIRST COAT Celanese Marco Resin Mil-2843.. rigid polyester. A V Celanese lsldarco R e s1 1\ 4 1 -30.-c-- iltexible polyester. Manufacturer Designation Constituents Parts by owmmu tyrene I 1 s yrene monomer v Volume Dow Corning. 1. Reichold .Polylite 8037 unsaturated polyester. 5 W Styrene yr monomer 5 25 20 parts parafiin wax, melting point 55 0.; 80 parts styrene monomer- Application ProcedureSpray one mil wet film, and allow it to penetrate into the wood.

SECOND COAT Specific Example 5 v3O Constituents Parts by Substrate-cement blocks Volume GROUNDCOAT 50% hydrogen peroxide 5 Parts Ethyl acetate 15 g Q by I Manufacturer Designation Constituents .wei gl t V or o Application Procedure Brush 1 mil wet film and allow to dry at 1 ume room temperature for 4 hour.

Hayden boron fluoride (satu- 10 TOP COAT rated solution). 40 Bakelite polyvinyl alcohol 10 Manufacturer Designation Constituents Parts by Volume Application Procedure-Brush V mil wet film, air dry A hour at room temperature. Polyllte 8037.. unsaturated polyester. styrene monomer 15 TOP COAT 45 P t Application Procedure-Spray two mil wet film and dry overnight at at 3 room temperature. This system forms a hard coating which sands Manufacturer Designatwn Constituents V easily. The grain of the plywood does not show through the finish. 0

Speczfic Example 3 Es. Rubbergtibrin lglfii fnutnsaturated polyester. 1%) Substrate-sanded walnut 0W yrene s yrene monomer T D id hit i eat 25 REACTIVE GROUNDCOAT ffi 'fi W e p gm cobaghsioiultigin a 1 a a s u on Manufacturer Designation Constituents Parts by p r o A Volume vThe pigment can be stirred into the polyester without resorting to the conventional dispersion techniques. Borden Polyco 117SS vmyl acetate latex 20 2 s f t te #1 Example 3 hydrogen p o de" 15 a See footnote #1, Example 4. V311 y 0WD D E Application Procedure-Brush two mil wet film. Air dry at temperament p tmture above F.

Application ProeedureSpray one mil wet film, air dry one hour at 1 10 parts 11% cobalt naphthanate; 90 parts styrene PIr-12-T.

2 Heat to dissolve.

Application ProcedureSpray two mil wet film, force dry 3 hours at 120 The coating forms a hard, dull film which sands easily and bufl's to a high gloss. The pores of the walnut were filled by this system and no separate filling operation was required.

Various examples of rather amazing results achieved with this technique in comparison to the results available by previously practiced methods and their more expensive and unstable catalysts are discussed in the following:

Unusual and decorative eifects can be obtained with some woods like Douglas Fir, spruce and pine which have a hard and soft grain by applying a 35% hydrogen peroxide. The water makes the soft springwood expand but does not affect the hard summerwood. When the wood has dried, the grain remains uneven, ester top coat holds the definitely.

Most finishes for furniture are rubbed and polished to provide a smooth even appearance and to bring out the grain. It is usually necessary to allow the furniture to and a polytion the polyester can stand overnight atroom temperature or about five hours at 120 F. before the finish is hard enough to rub and polish, and to minimize after-shrinkage. With conventionally catalyzed polyesters it is possible to rub and polish in about four hours at room temperature. With this invention it is possible to rub and polish in one hour or less. V

One of the problems with polyesters is the fact that they run easily when applied to a vertical surface. Most polyesters cannot be hot sprayed because it would reduce the pot life to almost nothing. However, with this invenbe hot sprayed with no fear of gelling, and you eliminate much of the problem of spraying on a vertical surface. Furthermore, with conventional polyesters where a catalyst is added before spraying, it is impossible to collect the overspray because it would gel before it could be reused. With this invention the overspray can be collected and used again.

What is claimed is:

1. A method of applying a polymerized coating of an unsaturated polyester upon a substrate which comprises the steps of applying a ground coat essentially consisting of an aqueous solution of hydrogen peroxide to said substrate, drying said ground coat, and applying said unsaturated polyester over said dried ground coat to rapidly cure said unsaturated polyester and form a polymerized coating over said substrate.

2. A method as set forth in claim .1 wherein a water miscible organic solvent is mixed into said aqueous solution of hydrogen peroxide to enhance its ability to spread over the substrate and to decrease the drying time.

3. A method as set forth in claim 1 wherein suitable water soluble thickeners are mixed into said aqueous solution of hydrogen peroxide to retard its penetration into said substrate.

4. A method as set forth in claim 1 wherein said aqueous solution of hydrogen peroxide is mixed with suitable water soluble film formers to retard its penetration into said substrate.

5. A method as set forth in claim 1 wherein said aqueous solution of hydrogen peroxide is mixed into the aqueous phase of an emulsion which retards its penetration into said substrate.

6. A method as set forth in claim 1 wherein said aqueous solution of hydrogen peroxide is mixed with an organic solvent solution of an organic solvent soluble film former which tolerates dissolved water over and above that required to dissolve said organic solvent soluble film former to retard its penetration into the substrate.

7. A method asset forth in claim 1 wherein said aqueous solution of hydrogen peroxide is applied to said substrate and allowed to dry, said substrate then being sanded and cleaned, and said unsaturated polyester being applied over said sanded and dried coating formed by said aqueous solution of hydrogen peroxide.

References Cited in the file of this patent UNITED STATES PATENTS 2,123,152 Rivat July 5, 1938 2,235,141 Dreyfus et a1 Mar. 18, 1941 2,424,284 Olpin July 22, 1947 2,440,318 White et al Apr. 27, 1948 2,515,340 Fisher et al. July 18, 1950 2,529,315 Serniuk Nov. 7, 1950 2,533,557 Chapman Dec. 12, 1950 2,599,943 Russel June 10, 1952 2,632,715 Nadeau et al. Mar. 24, 1953 2,684,305 Quinlivan July 20, 1954 2,704,753 Nonoghan Mar. 22, 1955 2,756,164 Fisher July 24, 1956 2,823,147 Upperman Feb. 11, 1958 2,930,106 Wrotnowski Mar. 29, 1960 Notice 0f Adverse Deeision in Interference In Interference N0. 92,? 9 involving Patent No. 2,978,354, D. K. Lesser, Method of applylng a coatlng, final udgment adverse to the patentee Was rendered June 13, 1968, as to claims 1, 2, 5, 6 and 7. 

1. A METHOD OF APPLYING A POLYMERIZED COATING OF AN UNSATURATED POLYESTER UPON A SUBSTRATE WHICH COMPRISES THE STEPS OF APPLYING A GROUND COAT ESSENTIALLY CONSISTING OF AN AQUEOUS SOLUTION OF HYDROGEN PEROXIDE TO SAID SUBSTRATE, DRYING SAID GROUND COAT, AND APPLYING SAID UNSATURATED POLYESTER OVER SAID DRIED GROUND COAT TO RAPIDLY CURE SAID UNSATURATED POLYESTER AND FORM A POLYMERIZED COATING OVER SAID SUBSTRATE. 